A one-pot conversion of alkyl azides to diazo compounds is outlined. After the reaction of α-azidocarbonyl compounds with Amphos, treatment of the resulting phosphazides with silica gel in a wet solvent afforded α-diazo carbonyl products. Through the azido group protection property of Amphos, inter- and intramolecular azide-site selective reactions of azido group protection, click functionalization, and deprotection of the diazo group have been demonstrated in one pot.